Substituted phthalocyanine dye developers and their use in multicolor diffusion transfer processes



DENSITY Decx9. 1969 E. M. IDELSON 3,482,972

SUBSTITUTED PHTHALOCYANINE DYE DEVELOPERS AND THEIR USE IN MULTICOLOR DIFFUSION TRANSFER PROCESSES Filed Dec. 28, 1967 30 REFLECTION DENSITY COMPARISON I,4-bis-(meihyl-B-hydroquinonyl-ethylumino)- 5,e-dihydroxyunthroquinone copper phtholocyonine 3, 3', 3", 3' 1mm hyroquinonyl isopropylumino sulfonomide) 2.5

WAVELENGTH IN MILLIMICRONS INVENTOR. (5W WZJ/ddwn BY 62am a/mi m m z wwm ATTORNEYS United States Patent 9 M 3,482,972 SUBSTITUTED PHTHALGCYANINE DYE DE- VELOPERS AND THEIR USE IN MULTI- COLOR DIFFUSION TRANSFER PROCESSES Elbert M. Idelson, Newton Lower Falls, Mass., assignor to Polaroid Corporation, Cambridge, Mass., 21 corporation of Delaware Filed Dec. 28, 1967, Ser. No. 694,167 Int. Cl. G03c 5/54, 5/26, 1/48 US. C]. 96-49 27 Claims ABSTRACT OF THE DISCLOSURE Novel phthalocyanine dye developers (-phthalocyanine dyes which are also silver halide developing agents) and also to photographic systems employing the same.

It is one object of the present invention to provide novel processes, products and compositions for the development of silver halide emulsions, in which novel colored silver halide developing agents are used to develop a latent photographic image.

Another object is to provide novel systems for the development of silver halide emulsions, in which colored developing agents develop a photographic latent image and impart a reversed or positive colored image of said latent image to a superposed image-receiving element.

A further object of this invention is to provide a novel class of compounds useful in photographic products, processes and compositions such as described and claimed in US. Patent No. 2,983,606, issued to Howard G. Rogers.

A further object is to provide novel products and processes suitable for use in preparing monochromatic and multichromatic photographic images.

Another object is to provide a novel class of phthalocyanine dyes which are also silver halide developing agents.

Still another object is to provide a cyan dye developer whose photographic images are of superior color.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others and the products possessing the features, properties and the relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which Will be indicated in the claims.

The novel photographic developing agents of this invention possess the properties of both a dye and a silver halide developing agent; thus they may be referred to as dye developers. The nature of these dye developers will be described hereinafter.

The photographic processes and compositions disclosed herein are particularly useful in the treatment of a latent image present in a photosensitive element, such as an exposed silver halide emulsion, whereby a positive dye image thereof may be imparted to another element, herein referred to as an image-carrying or image-receiving element.

US. Patent No. 2,983,606, issued May 9, 1961 to Howard G. Rogers, discloses diffusion transfer processes wherein a photographic negative material, such as a photographic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion layer a suitable liquid processing composition and bringing said emulsion layer into superposed relationship with an appropriate image-receiving layer.

3,482,972 Patented Dec. 9, 1969 It is an object of this invention to provide additional dye developers which give rise to transfer images of superior color characteristics and are suitable for use in such processes. The dye developers of this invention provide monochrome images of green, cyan and blue colors.

In carrying out the process of this invention, a photosensitive element containing a silver halide emulsion is exposed and Wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed, prior to, during or after Wetting, on an image-receiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive element is brought into superposed position with an image-receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently, at least in part, due to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It also may be due, in part, to a tanning effect on the emulsion by the oxidized developing agent. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer. Under certain circumstances, the layer of the liquid processing composition may be utilized as the image-receiving layer. The image-receiving layer receives a depthwise diffusion, from the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, to provide a reversed or positive, colored image of the developed image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. If the color of the diffused dye developer is affected by changes in the pH of the image-receiving element, this pH may be adjusted in accordance with well-known techniques to provide a pH affording the desired color. Imbibition periods of approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image is revealed by stripping the image-receiving element from the photosensitive element at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example, in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving element when in superposed relationship therewith. In this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing about 0.5 to 8% by weight of the dye developer. Similar concentrations may be used if the dye developer is utilized as a component of the liquid processing composition. In an especially useful mode of dispersing the dye developers in the photosensitive elements, the dye developer is dispersed in an alkaline solution permeable polymeric matrix wherein the mean particle size distribution of at least 50% and preferably at least 75% of the dye is below one micron in diameter. Reference is made to the copending application of Howard G. Rogers and Sidney Kasman, Ser. No. 659,370, filed Aug. 9, 1967, and now US. Patent No. 3,438,775.

The liquid processing composition above referred to comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain a minor amount of a conventional developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosity-increasing compound constituting the film-forming material of the type which, when said composition is spread and dried, will form a relatively firm and relatively stable film. A preferred film-forming material is a high molecular weight polymer such as a polymeric, water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other filmforming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be used.

The novel dye developers of this invention may be defined as phthalocyanines, or nuclear substituted derivatives thereof, containing at least one substituent comprising a disubstitutedphenyl silver halide developing radical linked to a phthalocyanine nucleus directly, or indirectly, through an appropriate divalent linking group in the manner known heretofore in the dye developer art. The phthalocyanines can be used in the metal-free form or in the form of complexes with metals known to form phthalocyanine complexes.

The term disubstitutedphenyl silver halide developing radical is intended to include dihydroxyphenyl, aminophenol, and diaminophenyl silver halide developing radicals, wherein the hydroxyl and/or amine groups present are situated ortho or para to each other.

The terms phthalocyanine(s) when used alone as either a noun or an adjective is intended to refer to both metallo and non-metallo phthalocyanine compounds.

The novel dye developers of this invention which contain a certral metal atom can be illustrated by the following formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R on any one benzene ring, the remaining R substituents being R groups, wherein R comprises a group (A) -E; A is a divalent organic linking radical, n is a number of from to 1 inclusive; E is an aryl group selected from the group consisting of benzene and naphthalene radicals so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups which are situated ortho or para to each other as to be capable of developing an exposed silver halide photographic emulsion; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the same or a different moiety selected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen. Typical examples of R moieties include: SO3H, Br, NH4, CH2C1, and SO3NH. Reference is made to Chapter 5 of Moser and Thomas, Phthalocyanine Compounds, Reinhold, copyright 1963.

The novel dye developers of this invention which do not contain a central metal atom can be illustrated by the following formula:

R N: R R ,t a

R NH R N -R E I i. 1's

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring, at least one and no more than four are as R groups, with not more than two R groups being on any one benzene ring, the remaining R substituents being R groups, wherein R R A, E and n are of the significance indicated at Formula A.

One preferred class of dye developers within Formula A comprises the compounds wherein the linking group between the phthalocyanine nucleus and a disubstitutedphenyl silver halide developing radical is wherein X and D are as defined indicated below.

Such compounds are represented by the formula:

( R if i II R o o R N N t N R R 11} \C R wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R is X is H or an alkyl group of 1-6 carbon atoms inclusive; D is an alkylene group of 1-6 carbon atoms inclusive; Q is a disubstitutedphenyl silver halide developing radical; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the same or a different moiety selected from the group consisting of monovalent organic and mono E K E I wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R is OH X X is H or CH and each R is the same or a different moiety selected from the group consisting of phenyl, alkyl, alkoxy, hydrogen, halogen, carboxyl and SO H.

The disubstitutedphenyl silver halide developing substituents and the divalent linking groups referred to above may be selected from those heretofore well-known in the art.

As examples of useful disubstitutedphenyl silver halide developing substituents, mention may be made of the following dihydroxyphenyl silver halide developing substituents; namely, ortho-dihydroxyphenyl, para-dihydroxyphenyl and nuclearsubstituted derivatives thereof, e.g., chloro, methyl, phenyl, and/or methoxy-substituted derivatives thereof, particularly nuclear-substituted pdihydroxyphenyls such as methylhydroquinonyl, pmethylphenylhydroquinonyl, chlorohydroquinonyl, methoxyhydroquinonyl, 2,6-dimethylhydroquinonyl, 2,6.-dimethoxy hydroquinonyl, 2 methoxy 6 methylhydroquinonyl, 2,3-dimethylhydroquinonyl, 2,5,6-trimethylhydroquinonyl, etc.

As examples of useful diaminophenyl and monoarnino, monohydroxyphenyl silver halide developing agents, mention may be made of any of the above dihydroxy substituents wherein one or both of the hydroxyl groups is replaced by -NH As examples of useful divalent linking groups joining the disubstitutedphenyl moiety to the designated position on the phthalocyanine moiety, mention may be made of the and linking groups described in U.S. Patent No. 3,288,778; aminophenalkylthio substituents such as disclosed in U.S. Patent No. 3,009,958; aminoalkylamino substituents such as disclosed in U.S. Patent No. 3,002,997; alkylthio substituents such as disclosed in U.S. Patent No. 3,043,690;

aminoalkyl substituents such as described in U.S. Patent No. 3,062,884; aminophenyl substituents such as disclosed in U.S. Patent No. 3,134,811; the acyl substituents disclosed in U.S. Patent No. 3,142,564; the aminophenoxy substituents such as disclosed in U.S. Patent No. 3,061,434; lower alkylene and the various other linking substituents disclosed in U.S. Patent No. 3,255,001, etc. Where the linking substituent is alkylene or contains an alkyl or alkylene moiety, the number of carbon atoms is preferably 1-4.

One method of preparing the novel dye developers of this invention comprises reacting a compound of the formula:

zi 3OH or a non-interfering substituted derivative thereof, with a metal chloride under suitable conditions in the presence of urea to obtain a Z-substituted metallo phthalocyanine compound. The metallo phthalocyanine is appropriately treated, if necessary, such as to render the Z substituent capable of being able to react with or be replaced by the substituent comprising the disubstitutedphenyl silver halide developing radical or a protected derivative of said radical. The nature of the appropriate treatment mentioned above 'will vary with the particular Z substituent utilized. Such procedures are seen to be within the skill of the art. The so-treated metallo phthalocyanine is then reacted with a compound which contains the disubstitutedphenyl silver halide developing radical or its protected derivative. A suitable metal chloride for use in this process is cupric chloride. The Z substituent on the compound, i.e., the phthalic acid, is H or a substituent which is or can be rendered capable of being reactive with or replaceable by the substituent comprising the disubstitutedphenyl silver halide developing radical to form the desired dye developer or a protected derivative thereof. Typical Z substituents include --SO H, Cl, COOH, NH- NCO',

CH Br, -H and Another method of preparing the novel compounds of the present invention is to react an unsubstituted preformed phthalocyanine, wherein the metallo or non-metallo moiety of the molecule, if present, is chosen from among the 46 metals known to form a metallo phthalocyanine, with a compound such as ClSO H, or an acyl halide, or the reaction product of CH O+HCl. These are capable of donating a substituent, Z, such as (SO Cl) or CO alkyl, or CH Cl upon reaction with said phthalocyanine such as to form a Z-substituted phthalocyanine,

wherein n is a number of from 1 to 16 and wherein the Z substituent is defined as previously noted with reference the Z-substituted phthalic acid. The Z-substituted phthalocyanine is appropriately treated, if necessary, such as to render the Z substituent capable of being able to react with or be replaced by the substituent comprising the disubstitutedphenyl silver halide developing radical or a protected derivative of said radical.

Several modes of preparing phthalocyanine compounds are set forth in detail in Phthalocyanine Compounds, Moser and Thomas, Reinhold Publishing Corporation. The compounds so prepared can be utilized to prepare the dye developers by the process set forth immediately above. As examples of dye developers Within the scope of this invention, mention may be made of:

III

XIX. O H

C} it? N R =N'C 00112011 (EH: (lug: 15 N-(%uN R: om-om-OH I C I I 1% h/ \l;

XX. R

l l 50 It will be appreciated that all of the compounds of the N=C C-li R formulae specified above exist in more than one isomeric form. Thus if the phthalocyanines without any substitu- R ents upon it were written in the form of a R='SO2N-CH OH with the circle signifying the central atom(s) and each of the four extremities signifying each of the four benzene moieties of the phthalocyanine ring which are capable of 0 b h h l b XXIL R su stitutlon, it is seen t at w en on y one posltlon 1s su stituted on each benzene nucleus such as in the formula:

G Q -Q N=C C-N C 65 c N which could be written as that there are four possible isomeric forms of such a compound. They are:

| I i L When each of the four benzene rings is substituted in only one position, but with a different substituent on each benzene ring, the number of isomers is increased many fold. The possible number of isomers becomes even more complex when there is more than one substituent on each benzene ring.

It is fully intended that all of the possible isomeric forms of the compounds set forth by formula Within the specification and in the appended claims are to be considered within the scope of the invention.

It will also be appreciated that in addition to the various isomers that exist for the several compounds, that many of the nonsymmetrical compounds, i.e., those wherein the su-bstituents on any of the four benzene nuclei differ, illustrate but one of a family or compounds. For example, if a mono-substituted phthalic acid is mixed with a di-substituted phthalic acid in the condensation step with the metal chloride, it is seen that the resulting metallo phthalocyanine can be all mono-substituted, all di-substituted or a part mono, part di-substituted compound.

Similarly, in the preformed phthalocyanine synthesis for these dye developers, the molar amount of the compound which donates the Z substituent and the reaction conditions will have a direct relation on the number of 2 substituents formed on the phthalocyanine.

It is fully intended that all of the various members of the families of the several compounds are to be included within the scope of this invention.

Compounds of the same structure except for a substitution of a different metal or a deletion of the metal and the replacement thereof by two hydrogen atoms show no subsantial color change.

It is known that phthalocyanine dyes that are unsubstituted have the ability to impart a cyan color to substances. When dye developers were prepared from such compounds, it was found that the nature of the group used to link the dye portion to the developer portion of the molecule could cause a color change toward green or blue from cyan. It was found that when certain moieties were used as the entire linking group or formed the part of the. linking group next adjacent to the phthalocyanine ring that this shift away from cyan was not experienced, regardless of the nature of the remainder of the linking group, provided that the remainder is nonchromophoric. The moieties which did not cause the color shift include but are not limited to:

a1kylene, arylene.

It was also noted that when normally cyan non-metallo and metallo phthalocyanine dye developers were substituted on their benzene nuclei, that the use of certain moieties as these substituents would cause a color change in the images obtained. However, moieties such as -SO =H, -SO NH SO NH alkyl, -alkyl and -aryl did not cause such a color change.

On the other hand the incorporation of such moieties into the molecule of a non-cyan phthalocyanine dye developer did not cause it to provide cyan images.

Dye developers which contain these non-color influencing moieties in the. manners indicated exhibit a greater absorption in the red portion of the spectrum and a lesser absorption in the green and blue portions of the spectrum than cyan anthraquinone dye developers, such as 1,4-bis- (a-methyl-fi-hydroquinonyl-ethylamino)-5,8 dihydroxyanthraquinone. Reference is made to the figure of the drawing wherein the phthalocyanine dye developer is copper phthalocyanine 3,3',3,3"-tetra[hydroquinonyl isopropyl, amino sulfonamide]. (See Formula VI, supra.)

In the figure, the curves representing the reflection density comparison are based on reflection spectra readings for diifusion transfer images placed in front of a spectrophotometric beam on a commercially available recording spectrophotometer. The reference standard utilized was a magnesium carbonate block. In accordance with techniques known in the art, readings were taken on the instrument and plotted. The spectrophotometn'c curves were chosen such that at the wavelengths of maximum absorption for each dye, the optical densities were equal. As can be seen on the spectrophotometric curves, the two compounds have an equal optical density at their individual maximum absorption peaks. The representative instantly claimed compound shows extremely good absorption in the 600-700 millimicron range, and lower absorption in the 380-600 millimicron range than the reference compound. Since the curve is lower in the 380-600 millimicron range for the representative claimed compound, it is seen that the curve more nearly approaches a perfect cyan compound curve which would show no absorption in this range. Therefore, the color obtained from the instant compounds is a better cyan.

When the instant compounds are placed in a multicolor subtractive color process environment, it is seen that better greens and blues will result relative to anthraquinone dyes, independent of optical density.

The novel dye developers of this invention have also been found to be extremely stable against the color degradation effects of light, humidity and/or heat.

The dye developers of this invention are seen to give difiusion transfer images which show substantial improvement in color stability to actinic radiation in comparison with cyan colored azo and anthraquinone dyes of similar optical density. Reference is made to the Light Stability data, infra, which compares the. aforementioned anthraquinone dye developer with two phthalocyanine dye developers.

Furthermore, these dye developers are not pH sensitive and are chemically stable in an aqueous alkaline processing medium.

The invention will be illustrated in greater detail in conjunction with the following specific examples which set out representative preparation and photographic utilization of the novel compounds of this invention, which, however, are not limited to the details therein set forth and are intended to be illustrative only.

EXAMPLE I To 42 grams of urea, heated to C., was added 42.3 grams of 4-sulfophthalic acid, said acid having been prepared by the evaporation of water from a 35% solution of the acid. 8 grams of copper chloride and 0.7 gram of H BO and 0.2 gram of (NH Mo O .4H O were also added. The mixture was heated gradually to 200 C. over a period of one hour until the urea melt became a solid mass. The mass was cooled and to this was added milliliters of C1SO H. 40 grams of PCl were gradually added. The contents of the vessel were heated at 130-l40 C. for one hour. The contents were allowed to cool to about 80 C. and 20 milliliters of thionyl chloride were added. The mixture was allowed to stand at room temperature for 15 hours. The contents were then poured over ice, the solid was filtered (faint yellow color), washed with water and dried. 5 grams of this intermediate product were combined with 50 milliliters of dimethyl 17 formamide and 10 milliliters, 0.036 mole of 1[2,5'-dimethoxyphenyl]-2-n1ethylan1inopropane of the forumla:

and heated to 60-65 C. for 1% hours. The mixture was then poured into a liter of dilute hydrochloric acid. The solid was filtered, washed with dilute hydrochloric acid and dried. 5 grams of this solid material was dissolved in 120 milliliters of methylene chloride and this solution was added slowly to 4.5 milliliters of BBr in 50 milliliters of methylene chloride. Stirring was continued for 30 minutes followed by the addition of sufiicient methanol to destroy the BBr The solid was filtered, redissolved in DMF and reprecipitated into a liter of dilute HCl. The solid was filtered, washed with dilute HCl and dried. The filter, wash and dry steps were repeated to insure purity.

Analysis of this product.Experimental: Cu, 4.28%; N, 9.98%; S, 8.64%; OCH 0.78%. Theoretical: Cu, 4.11%;'N, 10.85%; S, 8.26%; OCH 0.00%.

The spectral absorption curve of this product exhibits a X at 679 in DMF, e=155,000; and a A at 610 millimicrons with an e of 36,600.

EXAMPLE II grams of copper phthalocyanine was added to 180 grams of chlorosulfonic acid and stirred. grams of phosphorous pentachloride was added gradually to the mixture to avoid foaming. The mixture was heated to 130-135 C. for 1% to 1% hours. It was then poured over crushed ice. The blue solid was filtered and dried. A sample of the blue solid was found to be insoluble in methyl Cellosolve and also in water, while the filtrate was found to be clear and almost colorless. The blue solid was copper phthalocyanine tetrasulfonyl chloride. 30 grams of this product prepared in the manner described above were dissolved in 300 milliliters of dimethyl formamide. 60 milliliters, (0.03 mole) of 1[2,5'-dime thoxyphenyl] -2-aminopropane which has the formula:

E HNCH was added to the solution with stirring. The mixture was heated to about 6515 C. for about 2 hours. At that time, the solution was cooled to room temperature and poured into 3 liters of dilute 3 normal HCl. A blue precipitate was formed. The solid was filtered, dried and redissolved in a minimal amount of hot DMF. The solid was reprecipitated by pouring this into a large excess of dilute hydrochloric acid. The solid was filtered, washed with dilute acid and dried to a blue solid.

milliliters (66.4 grams) of boron tribromide was added to 300 milliliters of methylene chloride. 33 grams of the blue solid product was ground to a fine powder and dissolved in 600 milliliters of methylene chloride with constant stirring. This blue solution was added dropwise into the rapidly stirring boron tribromide-methylene chloride solution. This mixture assumed a green color and a solid separated. After 2 hours of stirring, the excess boron tribromide was destroyed by the careful addititon of 100 cc. of methanol. The mixture was filtered and a blue solid was isolated which was then dissolved in a minimal amount of hot DMF, and reprecipitated by pouring the solution into a large excess of dilute hydrochloric acid.

18 The blue solid was filtered, dried well, ground up and stirred for at least one hour in 300 cc. of dilute HCl. It was refiltered, washed with dilute HCl and dried.

Analysis of this pr0duct.Experimental: Cu, 4.40%; N, 11.18%; S, 8.67%; OCH 0.17%. Theoretical: Cu, 4.25%; N, 11.22%; S, 8.56%; OCH 0.00%.

The spectral absorption curve of this product exhibits a A at 611 millimicrons in pyridine, e=34,600; A 680 millimicrons in DMF, 6: 176,000.

It is to be seen that the amines utilized in the two processes set forth in Examples I and 11 above are interchangeable for each other in the two processes. When such experiments are conducted, similar results, as were obtained in Examples I and II, were achieved.

The novel dyes of this invention are characterized in that they contain not less than one benzenoid developing group and as such are useful dye developers. In the following example all parts are given by weight except where otherwise noted, and all operations involving light-sensitive materials are carried out in the absence of actinic radiation. These examples are intended to be illustrative only of the photographic use of the dye developers and should not be construed as limiting the invention in any way.

EXAMPLE III Water cc KOH g 11.2 Hydroxyethyl cellulose g 3.8 Benzotriazole g 3.5 Potassium thiosulfate g 0.5 N-benzyl-a-picolinium bromide g 2.0 Zinc nitrate g 0.5 Lithium nitrate g 0.5

The image-receiving element comprised baryta paper coated with a layer of a partial butyl ester of poly-(ethylene/maleic anhydride), followed by a layer of polyvinyl alcohol and a layer of a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine. Image-receiving elements of this type are disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 234,- 864, filed Nov. 1, 1962. After an imbibition period of approximately one minute, the image-receiving element was separated and contained a cyan positive image having a d of 0.26 and a d of 0.14.

The same photosensitive element when processed in the same manner except with a 0.2% MPHQ processing composition had a a of 0.20 and a d of 0.11.

EXAMPLE IV acetate hydrogen phthalate in acetone. After this coating dried, a red-sensitive silver iodobromide emulsion was coated on at a speed of 5 feet per minute and allowed to dry. This photosensitive element was exposed and processed by spreading, between the thus exposed photosensitive element and a superposed image-receiving element, the aqueous processing composition set forth in EX- ample III, namely:

The image-receiving element comprised baryta paper coated with a layer of a partial butyl ester of poly(ethylene/maleic anhydride), followed by a layer of polyvinyl alcohol and a layer of a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine. Image-receiving elements of this type are disclosed and claimed in the copending application of Edwin H. Land, Ser. No. 234,864, filed Nov. 1, 1962, now U.S. Patent No. 3,362,- 819. After an imbibition period of approximately one minute, the image-receiving element was separated and contained a cyan positive image having a. d of 0.75 and a d of 0.45.

The same photosensitive element when processed in the same manner except with a 0.2% 4'-methylphenylhydroquinone processing composition had a d of 0.85 and a (1 m Of The novel dye developers of this invention exhibit increased stability against the color degradation eifects of actinic radiation, humidity and/0r heat.

Positive dye images prepared in the manner described in Examples III and IV were subjected to standard accelerated fading tests and the percent of fading was noted after several dosages of radiation. The fading tests were conducted under a Xenon arc intensity of 128-130 F. with infrared light filtered out at a 12" lamp to subject distance in the presence of 31% relative humidity.

The following tables illustrate the increased stability of the novel dye developers of this invention.

TABLE I.-PERCENT FADING hours hours hours hours Dye developer of Example III 1 4 12 13 Sample I of Control 8 13 2O 39 The Control was a cyan dye developer of the formula l,4,-bis-(amethyl-B-hydroquinonyl-ethylamino)-5,8-dihydroxyanthraquinone (the preparation of which is described in U.S. Patent No. 3,135,606, issued to Blout et al. on June 2, 1964 and in U.S. Patent No. 3,209,016, issued to Blout et al. on Sept. 28, 1965).

TABLE IL-PERCENT FADING hours hours hours hours Dye Developer of Example IV 9 12 14 15 Sample II of Control" 4 10 17 32 See footnote at end of Table I.

EXAMPLE V A photosensitive element was prepared by dispersing 1.0 g. of copper phthalocyanine, 3,3',3",3"-tetra(dihydroxyphenyl isopropylamino sulfonamide) in water containing 10% dispersing agent, Lomar D, a sodium salt of a condensed mononaphthalene sulfonic acid, based on dye solids. This mixture was agitated by means of a Branson sonifier for one hour. An aqueous solution of 2.0 g. of 5% Gantrez AN-169 (a copolymer of ethylene maleic anhydride and methyl vinyl ether), was added to this dispersion and the resulting dye dispersion was added to enough water and wetting agents to be coated on a cellulose triacetate film base at a coverage of 123.5 mg. per square foot of dye. After this coating dried, a red-sensitive silver iodobromide emulsion was coated at a coverage of 222 mg. per square foot of silver on this and allowed to dry. This photosensitive element was exposed and processed by spreading, between the thus exposed photosensitive element and a superposed image-receiving element, an aqueous processing composition comprising:

Water cc NaOH g-.. 6.8 Hydroxyethyl cellulose g 3.8 Benzotriazole g 3.5 Potassium thiosulfate g 0.5 N-benzyl-u-picolinium bromide g 2.0 Lithium nitrate g 0.5 Zinc nitrate g 0.5

The image-receiving element comprised baryta paper coated with a layer of a partial butyl ester of poly- (ethylene/maleic anhydride), followed by a layer of polyvinyl alcohol and a layer of a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine. After an imbibition period of approximately one minute, the imagereceiving element was separated and contained a cyan positive image having a d of 2.40 and a d of .50.

The dye developers of this invention are useful in integral multilayer photosensitive elements intended for use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in U.S. Patent No. 3,345,163, issued Oct. 3, 1967 to Edwin H. Land and Howard G. Rogers, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively a cyan dye developer, :1 magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, or a similar camera structure such, for example, as the camera forming the subject matter of U.S. Patent No. 2,435,717, issued to Edwin H. Land on Feb. 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be superposed on the image-receiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well-known to the art. See, for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenyl (Metol); 2,4-diaminophenol (Amidol); benzylaminophenol; hydroquinone; a substituted hydroquinone such.

as toluhydroquinone, phenylhydroquinone, or 4-methylphenylhydroquinone; or a S-pyrazolidone such as 1- phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in U.S. Patent No. 3,173,786, issued Mar. 16, 1965 to Milton Green and Howard G. Rogers.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black and white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 12% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sufficient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called autocoupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of imagereceiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, mention may be made of nylon, e.g., N-methoxymethylpolyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restainer, e.g., 1-phenyl-S-mercaptotetrazole, as disclosed in US. Patent No. 3,265,498, issued Aug. 9, 1966 to Howard G. Rogers and Harriet W. Lutes.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US. Patent No. 2,968,554, issued to Edwin H. Land on Jan. 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibers, such as nylon.

In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black, as well as the use of a single black dye developer.

Since certain changes may be made in the above products, compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limit ing sense.

What is claimed is:

1. A photographic developer composition comprising an aqueous alkaline solution containing a silver halide auxiliary developing agent which is substantially colorless, at least in its unoxidized form, and a phthalocyanine dye containing at least one substituent comprising a dihydroxyphenyl or amino-hydroxy-phenyl silver halide developing radical.

2. A photographic developer composition comprising an aqueous alkaline solution containing a silver halide auxiliary developing agent which is substantially colorless, at least in its unoxidized form, and a dye developer of the formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring :at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R comprises a group (A),,E; A is a divalent organic linking radical; n is a number of from 0 to 1; E is an aryl group selected from the group consisting of benzene and naphthalene radicals so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups which are situated ortho or para to each other as to be capable of developing an exposed silver halide photographic emulsion; M is l3. metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the same or a different moiety se lected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen.

3. A photographic developer composition as defined in claim 2 wherein the dye developer is of the formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four areas R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R is X -S02l TDQ X is selected from the group consisting of hydrogen and an alkyl group of l6 carbon atoms inclusive; D is an alkylene group of l-6 carbon atoms inclusive; Q is a dihydroxyphenyl silver halide developing radical; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the some or a different moiety selected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen.

4. A photographic developer composition as defined in claim 2 wherein the dye developer is of the formula:

5. A photographic developer composition as defined in claim 2 wherein the dye developer is of the formula:

6. A photographic product comprising a support carrying on one side thereof a plurality of layers, at least one of said layers containing a silver halide emulsion and at least one of said layers containing a dye developer, said dye developer being a phthalocyanine dye containing at least one substituent comprising a dihydroxyphenyl or amino-hydroxy-phenyl silver halide developing radical.

7. A photographic product comprising a support carrying on one side thereof a plurality of layers, at least one of said layers containing a silver halide emulsion, and at least one of said layers containing a dye developer, said dye developer being a compound of the formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents Ebeing R groups, wherein R comprises a group (A) E; A is a divalent organic linking radical; n is a number of from 0 to 1; E is an aryl group selected from the group consisting of benzene and naphthalene radicals so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups which are situated ortho or para to each other as to be capable of developing an exposed silver halide photographic emulsion; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the same or a different moiety selected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen.

8. A photographic product as defined in claim 7 wherein the dye developer is a compound of the formula:

wherein it is provided that of the 16 R substituents pres ent on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R is X is selected from the group consisting of hydrogen and an alkyl group of 1-6 carbon atoms inclusive; D is an alkylene group of 1-6 carbon atoms inclusive; Q is a dihydroxyphenyl silver halide developing radical; M is a metal selected from the group consisting of cobalt nickel,

9. A photographic product as defined in claim 7 wherein the dye developer is a compound of the formula:

11. A photographic product as defined in claim 7 wherein the dye developer is a compound of the for- 26 12. A photographic product as defined in claim 7 wherein the dye developer is a compound of the formula:

13. A process of developing an exposed photosensitive silver halide emulsion which comprises treating said emulsion with an aqueous alkaline solution of a phthalocyanine dye which contains at least one substituent comprising a dihydroxyphenyl or amino-hydroxy-phenyl halide developing radical.

14. A process of developing an exposed photosensitive silver halide emulsion which comprises treating said emulsion with an aqueous alkaline solution of a dye developer which is a compound of the formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R comprises a group (-A) E; A is a divalent organic linking radical; n is a number of from 0 to l; E is an aryl group selected from the group consisting of benzene and naphthalene radicals so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups which are situated ortho or para to each other as to be capable of developing an exposed silver halide photographic emulsion; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the same or a difierent moiety selected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen.

15. A process of developing an exposed photosensitive silver halide emulsion which comprises treating said emul- 27 sion with an aqueous alkaline solution of a dye developer which is a compound of the formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R is X is selected from the group consisting of hydrogen and an alkyl group of 1-6 carbon atoms inclusive; D is an alkylene group of l-6 carbon atoms inclusive; Q is a dihydroxyphenyl silver halide developing radical; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesium and zinc; and each R comprises the same or a different moiety selected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen.

16. A process of developing an exposed photosensitive silver halide emulsion which comprises treating said emulsion with an aqueous alkaline solution of a dye developer which is a compound of the formula:

17. A process of developing an exposed photosensitive silver halide emulsion which comprises treating said emulsion with an aqueous alkaline solutionof a dye developer which is a compound of the formula:

18. In a process of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of a phthalocyanine dye developer, oxidizing said dye developer as a function of the point-to-point degree of development, forming in undeveloped areas of said silver halide emulsion an imagewise distribution of unoxidized dye developer and transferring at least part of said imagewise distribution of unoxidized dye developer, by imbibition, from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart a dye transfer image to said image-receiving layer.

19. In a process of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of a dye developer compound having the formula:

wherein it is provided that of the 16 R substituents present on the phthalocyanine ring at least one and no more than four are as R groups, there being no more than two R groups on any one benzene ring, the remaining R substituents being R groups, wherein R comprises a group (A),,E; A is a divalent organic linking radical; n is a number from O to 1; E is an aryl group selected from the group consisting of benzene and naphthalene radicals so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups which are situated ortho or para to each other as to be capable of developing an exposed silver halide photographic emulsion; M is a metal selected from the group consisting of cobalt, nickel, copper, chromium, magnesiurn and zinc; and each R comprises the same or a dilferent moiety selected from the group consisting of monovalent organic and monovalent inorganic radicals, neither of which contain a silver halide developing radical, and hydrogen, oxidizing said dye developer as a function of the point-to-point degree of development, forming in undeveloped areas of said silver halide emulsion an imagewise distribution of unoxidized dye developer and transferring at least part of said imagewise distribution of unoxidized dye developer, by imbibition, from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart a dye transfer image to said image-receiving layer.

20. The process as defined in claim 19 wherein said dye developer is dispersed prior to exposure in a photosensitive element comprising said silver halide emulsion, and including the step of permeating said photosensitive element with an aqueous alkaline liquid capable of soluhilizing said dye developer.

21. The process as defined in claim 20 wherein said liquid is introduced by being spread in a substantially uniform layer between said photosensitive element and an image-receiving element comprising said image-receiving layer as said elements are brought into superposed relationship.

22. The process as defined in claim 21 wherein said liquid contains a thickener for increasing viscosity and for facilitating the spreading thereof between said photosensitive element and said image-receiving element.

23. The process as defined in claim 19 wherein said dye developer is dissolved in an aqueous alkaline solution prior to application of said solution to said exposed emulsion.

24. A process of forming photographic images in color as defined in claim 19 wherein the dye developer is a compound of the formula:

Ill

i= f i C C W N R U N-Ci. N R

\ N o o .u/ \l OH I R=SOzI I-CHCH 25. A process of forming photographic images in color as defined in claim 19 wherein the dye developer is a compound of the formula:

67' N=o o R 0 N N-(iu-N\ 70 N o o l, u

26. A process of forming photographic images in color as defined in claim 19 wherein the dye developer is a compound of the formula:

27. A process of forming photographic images in color as defined in claim 19 wherein the dye developer is a compound of the formula:

Cu-N R gr i i N=C (w-bk R=CH2CH I OH References Cited UNITED STATES PATENTS 2,884,326 4/1959 Zemp 9649 2,915,392 12/1959 Pedersen .96-27 2,983,606 5/1961 Rogers 9629 3,178,285 4/1965 Anderau et al. 9673 FOREIGN PATENTS 974,715 10/1950 France.

NORMAN G. TORCHIN, Primary Examiner ALFONSO T. SURO PICO, Assistant Examiner US. Cl. X.R. 9649; 260314.5 

